In the past few years, many nanocomposites thin films have been achieved by the advanced metal-organic aerosol deposition or pulsed laser deposition (PLD) technique, such as BaTiO 3 -CoFe 2 O 4 , [17] (La 0.7 Sr 0.3 MnO 3 ) 1-x :(MgO) x , [18] (La 0.7 Ca 0.3 MnO 3 ) 1-x :(MgO) x , [19] and (La 0.7 Sr 0.3 MnO 3 ) 0.5 :(ZnO) 0.5 nanocomposites. [20] For example, tunable metal-insulator transition has been realized previously in La 2/3 Sr 1/3 MnO 3 (LSMO)-V 2 O 3 nanocomposites by engineering the relative chemical ratio between LSMO and V 2 O 3 during PLD growth. [21] The functionalities of the nanocomposites film are determined by the structure and chemistry of nanoscale phases and the interfaces between them. The interfaces can have a strong impact on the lattice distortion, spin-orbital-charge coupling and electron scattering, and thus finally generate novel phenomena as occurring in the planar heterostructures. [22,23] Therefore, the investigations on the nanoscale structures and their interfaces, chemistry, and electronic structures are crucial for not only revealing the mechanism of nanocomposite formation but also understanding the underlying structure-property relation, which consequently will guide us the control of nanocomposite growth and as a result the functionality engineering for device applications. However, the buried interfaces in nanocomposites are usually diffuse, rough, and/or heterogeneous, [24][25][26] making it very difficult to extract the atomic bonding information and chemistry of interfaces.In this paper, we study the microstructure of nanocomposite (LaSr)(MnV)O 3 (LSMVO) thin films using the aberration-corrected scanning transmission electron microscopy (Cs-STEM) and electron energy loss spectroscopy (EELS). We find that the epitaxial grown LSMVO thin-film matrix is embedded with two types of self-assembled columnar composite oxides, i.e., MnO and V 2 O 3 nanopillars. The structure and composition of these nanopillars are identified. The atomic bonding and electronic structures at the heterointerfaces of LSMVO/MnO and LSMVO/V 2 O 3 are determined. Our findings provide deep insights into the growth mechanism of the nanocomposite and the understanding of the structure driven novel transport properties in these films.